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  • B01J2531/48—Zirconium
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Definitions

• the invention relates to catalysts useful for olefin polymerization.
• the catalysts incorporate dianionic indenoindolyl ligands and at least one Group 3-10 transition or lanthanide metal atom.
• Metallocenes typically include a transition metal and at least one cyclopentadienyl or substituted cyclopentadienyl ligand. More recently, a number of non-metallocene, single-site catalysts have also been reported. Some of these catalysts replace the cyclopentadienyl groups of metallocenes with one or more heteroatomic ring ligands such as boraaryl (U.S. Pat. No. 5,554,775), indolyl or pyrrolyl (U.S. Pat. No. 5,539,124), or azaborolinyl groups (U.S. Pat. No. 5,902,866).
• boraaryl U.S. Pat. No. 5,554,775
• indolyl or pyrrolyl U.S. Pat. No. 5,539,124
• azaborolinyl groups U.S. Pat. No. 5,902,866
• Organometallic complexes that incorporate one transition metal and at least one indenoindolyl ligand have also been described (see PCT Int. Appl. WO 99/24446 and copending Appl. Ser. No. 09/417,510, filed October 14, 1999). These complexes are normally made by reacting a transition metal source (e.g., zirconium tetrachloride) with one or two equivalents of an indenoindolyl monoanion. The monoanion is conveniently made by reacting a suitable precursor with about one equivalent of a potent base, such as n-butyllithium or methylmagnesium bromide.
• a transition metal source e.g., zirconium tetrachloride
• the monoanion is conveniently made by reacting a suitable precursor with about one equivalent of a potent base, such as n-butyllithium or methylmagnesium bromide.
• Deprotonation removes an acidic proton from the methylene carbon of the cyclopentadiene fragment: strong base
• the indenoindolyl monoanion is a ⁇ -electron donor ligand that can displace labile anionic groups (e.g., a halide) from a transition metal compound to produce an indenoindolyl metal complex:
• R is usually an alkyl or aryl group.
• R is almost exclusively methyl or phenyl.
• R is methyl (see Examples A and B).
• the reported complexes are normally combined with an activator, such as methyl alumoxane, and are then used to polymerize olefins such as ethylene, or mixtures of ethylene and other -olefins.
• the invention is an organometallic complex which comprises at least one Group 3-10 transition or lanthanide metal and at least one dianionic indenoindolyl ligand that is pi- or sigma-bonded to the metal.
• the invention includes complexes produced from a dianionic indenoindolyl ligand that is generated from a synthetic equivalent.
• Catalyst systems of the invention comprise the complex and an activator, which is preferably an alkyl alumoxane. Also included is a method which comprises polymerizing an olefin in the presence of a catalyst system of the invention.
• Indenoindolyl dianions and their synthetic equivalents are remarkably versatile. As described below, they can be used to produce a diverse assortment of monomeric, dimeric, and even polymeric or zwitterionic complexes that incorporate one or more transition metal atoms or a combination of transition metal and Group 13 atoms. When used with an activator, the complexes are valuable olefin polymerization catalysts.
• Organometallic complexes useful for catalyst systems of the invention comprise at least one Group 3-10 transition or lanthanide metal atom and at least one dianionic indenoindolyl ligand.
• Preferred complexes include a Group 4 to 6 transition metal; most preferably, the complex contains a Group 4 metal such as titanium or zirconium.
• Dianionic indenoindolyl ligands are produced by reacting two equivalents of a potent base with an indenoindole compound.
• indenoindole compound we mean an organic compound that has both indole and indene rings. The five-membered rings from each are fused, i.e., they share two carbon atoms. Preferably, the rings are fused such that the indole nitrogen and the only sp -hybridized carbon on the indenyl ring are "trans" to each other.
• an indeno[1 ,2-b] ring system such as:
• Suitable ring systems also include those in which the indole nitrogen and the sp 3 -hybridized carbon of the indene are beta to each other, i.e., they are on the same side of the molecule.
• the ring atoms can be unsubstituted or substituted with one or more groups such as alkyl, aryl, aralkyl, halogen, silyl, nitro, dialkylamino, diarylamino, alkoxy, aryloxy, thioether, or the like. Additional fused rings can be present, as long as an indenoindole moiety is present.
• indenoindole When used to make a dianionic ligand, it must have both an unsubstituted nitrogen (i.e., it has a hydrogen atom attached to nitrogen) and at least one hydrogen atom on the indenyl methylene carbon. Numbering of indenoindoles follows IUPAC Rule A-22. The molecule is oriented as shown below, and numbering is done clockwise beginning with the ring at the uppermost right of the structure in a manner effective to give the lowest possible number to the heteroatom. Thus, 5,10-dihydroindeno[1 ,2-b]indole is numbered as follows:
• Suitable indenoindole compounds that are precursors to indenoindolyl dianions and their synthetic equivalents include, for example, 5,10-dihydroindeno[1 ,2-b]indole, 5,6-dihydroindeno[2,1- b]indole, 4,7-dimethyl-5,10-dihydroindeno[1 ,2-b]indole, 4-tert-butyl-8- methyl-5,10-dihydroindeno[1 ,2-b]indole, 4,8-dichloro-5,10-dihydroindeno- [1 ,2-b]indole, 2,7-dimethyl-5,6-dihydroindeno[2,1-b]indole, and the like.
• indenoindole compounds are well known. Suitable methods are disclosed, for example, in copending Appl. Ser. No. 09/417,510, and references cited therein, including the method of Buu- Hoi and Xuong, J. Chem. Soc. (1952) 2225. Suitable procedures also appear in PCT Int. Appl. WO 99/24446. Indenoindolyl dianions can be generated by deprotonating an indenoindole compound with two equivalents of a strong base.
• Suitable bases include alkali metals (e.g., sodium or potassium), alkali metal hydrides (sodium hydride, lithium hydride), alkali metal aluminum hydrides (lithium aluminum hydride), alkali metal alkyls (n-butyllithium), Grignard reagents (methyl magnesium bromide, phenyl magnesium chloride), and the like.
• the deprotonation step is normally performed at or below room temperature, preferably at about room temperature, by combining the indenoindole compound and the deprotonating agent, usually in the presence of one or more dry organic solvents, especially ethers and/or hydrocarbons.
• Suitable methods for generating dianionic indenoindolyl ligands are also disclosed by T. Abraham et al. in Monatsh. Chem. 120 (1989) 117 and Tetrahedron 38 (1982) 1019.
• two equivalents of n-butyllithium are added slowly to an ice- cooled solution of the indenoindole in dry tetrahydrofuran to generate a blood-red solution of the dianion.
• the first equivalent of base deprotonates the nitrogen atom and creates a sigma-electron donor center at nitrogen:
• Reaction of the dianion with transition metal sources gives a complex that normally contains one or more indenoindolyl dianionic ligands that are ⁇ - and/or ⁇ -bonded to the transition or lanthanide metal.
• the indenoindolyl dianion preferably has a structure selected from:
• M is a Group 1 (alkali) or Group 2 (alkaline earth) metal.
• the invention contemplates the use of synthetic equivalents of indenoindolyl dianions in making the organometallic complexes.
• synthetic equivalent of an indenoindolyl dianion, we mean a “masked” dianion. While not an indenoindolyl dianion per se, the synthetic equivalent has the ability to deliver one when reacted with a transition metal source (such as zirconium tetrachloride or cyclopentadienyltitanium trichloride).
• a transition metal source such as zirconium tetrachloride or cyclopentadienyltitanium trichloride.
• Suitable synthetic equivalents replace one or two acidic hydrogens from an indenoindole compound with an organosilicon, organotin, or organogermanium group.
• Examples (a)-(f) below illustrate various synthetic equivalents of indenoindolyl dianions.
• M is an alkali metal
• each of R and R' is independently selected from the group consisting of organotin, organosilicon, and organogermanium.
• suitable synthetic equivalents of the dianions can be neutral compounds that contain two organotin, -silicon, or -germanium groups; they can also be monoanionic compounds that have a single organotin, -silicon, or -germanium group.
• the synthetic equivalents can be made by numerous techniques. Some of these are described by Abraham et al. (see, especially, Scheme 3 in Monatsh. Chem. 120 at p. 122). Usually, a stepwise approach is used. In one suitable method, an indenoindolyl N-centered monoanion is generated and reacted with chlorotrimethylsilane. (Optionally, the mixture is quenched with water and the N-silylated product is isolated.) Reaction with a second equivalent of base, typically n-butyllithium or the like, followed by reaction with another equivalent of chlorotrimethylsilane gives the desired disilylated product, which is a dianion synthetic equivalent:
• a dianion is generated first, for example, with two equivalents of n-butyllithium. Reaction with one equivalent of chlorotrimethylsilane masks the more reactive cyclopentadienyl anion. (Again, the mixture is optionally quenched with water to isolate the C-silylated product.) Reaction with a second equivalent of chlorotrimethylsilane gives the same dianion synthetic equivalent:
• Organometallic complexes of the invention are reaction products of a Group 3-10 transition or lanthanide metal compound and a dianionic indenoindolyl ligand or its synthetic equivalent.
• the Group 3-10 transition or lanthanide metal compound usually includes two or more labile anionic or neutral ligands that can be replaced by one or more indenoindolyl groups.
• Any convenient source of the Group 3 to 10 transition or lanthanide metal can be used.
• the source is a complex that contains one or more labile ligands that are easily displaced by the indenoindolyl dianion or synthetic equivalent. Examples are halides (e.g., TiCI 4 , ZrCI ), alkoxides, amides, and the like.
• the metal source can incorporate one or more of the polymerization-stable anionic ligands described below.
• organometallic complexes can be made from indenoindolyl dianions and their equivalents. For example, monomeric, dimeric, or even polymeric organometallic complexes can be produced.
• the complexes can be mono-, bi-, or multimetallic.
• the complexes can exist in zwitterionic forms, and they can incorporate Group 13 atoms such as boron or aluminum.
• One preferred complex has the structure:
• each Z is a Group 4 transition metal
• each L independently represents a pi-donor ligand
• each X independently represents a sigma-donor ligand
• Preferred pi-donor ligands, L include cyclopentadienyls, indenyls, fluorenyls, azaborolinyls, indolyls, and the like. These ligands are normally characterized as "polymerization stable" because they remain coordinated to the transition metal during olefin polymerizations. These and other suitable pi-donor ligands are described in U.S. Pat. Nos. 4,791 ,180 and 4,752,597.
• Suitable sigma-donor ligands, X are normally labile groups such as halide, hydride, alkyl, aryl, aralkyl, alkoxy, aryloxy, dialkylamino, siloxy, or the like. Halides are preferred.
• the organometallic complex can be essentially a dimer that incorporates two transition metal atoms and two indenoindolyl ligands.
• Such catalysts are conveniently made by reacting one equivalent of dianionic ligand or its equivalent with one equivalent of transition metal compound.
• Preferred complexes of this type have a structure selected from:
• polymeric complexes can comprise a minor or major portion of the reaction product.
• reaction conditions By modifying the reaction conditions, a skilled person can manipulate the proportion of dimer to polymeric complex to be produced.
• a preferred polymeric complex has the structure:
• n has a value from about 2 to about 100.
• Additional organometallic complexes of the invention comprise the reaction product of a Group 3-10 transition or lanthanide metal compound, a Group 13 compound, and a dianionic indenoindolyl ligand or its equivalent.
• One preferred complex of this type, which has one indenoindolyl group, has a structure selected from:
• M is an alkali metal
• Z, L, and X have the meanings defined earlier
• A is a Group 13 element.
• these complexes are made by first reacting the nitrogen-centered monoanion with a Group 13 compound followed by deprotonation at the cyclopentadienyl fragment with a bulky base such as t-butyllithium, lithium diisopropylamide, 2,2,6,6- tetramethylpiperidinyl lithium, or the like. Subsequent reaction with a molar equivalent of the Group 3-10 (preferably Group 4) transition or lanthanide metal compound gives the desired bimetallic complex (a) above, and/or its quaternized equivalent (b).
• Suitable Group 13 compounds are well known. These preferably have the formula BX 3 or AIX 3 wherein each X independently represents a labile sigma-donor ligand such as halide, hydride, alkyl, aryl, aralkyl, alkoxy, aryloxy, dialkylamino, siloxy, or the like. Halides and alkyls are preferred. Typical examples are chlorodimethylborane, chlorodiphenyl- borane, diethylalurninum chloride, triethylaluminum, ethylaluminum dichloride, and the like.
• Complexes containing two indenoindolyl groups, a Group 13 element, and a Group 3-10 (preferably Group 4) element can also be made.
• Preferred complexes in this category have a structure selected from:
• Additional complexes incorporate a Group 3-10 transition or lanthanide metal, two Group 13 atoms, and two dianionic indenoindolyl ligands.
• Preferred complexes in this category have a structure selected from: (a) and (b)
• polymeric complexes By adjusting the reaction conditions and proportions of reactants, polymeric complexes can also be made.
• Preferred polymeric complexes of this type have a structure selected from:
• n has a value from about 2 to about 100.
• Catalyst systems of the invention comprise the organometallic complex and an activator.
• Suitable activators ionize the organometallic complex to produce an active olefin polymerization catalyst.
• Suitable activators are well known in the art. Examples include alkyl alumoxanes (methyl alumoxane (MAO), PMAO, ethyl alumoxane, diisobutyl alumoxane), alkylaluminum compounds (triethylaluminum, diethyl aluminum chloride, trimethylaluminum, triisobutyl aluminum), and the like.
• Suitable activators include acid salts that contain non-nucleophilic anions.
• These compounds generally consist of bulky ligands attached to boron or aluminum.
• Examples include lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)aluminate, anilinium tetrakis(penta- fluorophenyl)borate, and the like.
• Suitable activators also include organoboranes, which include boron and one or more alkyl, aryl, or aralkyl groups.
• Suitable activators include substituted and unsubstituted trialkyl and triarylboranes such as tris(pentafluorophenyl)borane, triphenylborane, tri-n-octylborane, and the like. These and other suitable boron-containing activators are described in U.S. Pat. Nos. 5,153,157, 5,198,401 , and 5,241 ,025. Alkyl alumoxanes such as MAO are most preferred.
• the amount of activator needed relative to the amount of organometallic complex depends on many factors, including the nature of the complex and activator, the desired reaction rate, the kind of polyolefin product, the reaction conditions, and other factors. Generally, however, when the activator is an alkyl alumoxane or an alkyl aluminum compound, the amount used will be within the range of about 0.01 to about 5000 moles, preferably from about 0.1 to about 500 moles, of aluminum per mole of transition metal. When the activator is an organoborane or an ionic borate or aluminate, the amount used will be within the range of about 0.01 to about 5000 moles, preferably from about 0.1 to about 500 moles, of activator per mole of transition metal. If desired, a catalyst support such as silica or alumina can be used. However, the use of a support is generally not necessary for practicing the process of the invention.
• the catalysts are particularly valuable for polymerizing olefins.
• Preferred olefins are ethylene and C 3 -C 2 o ⁇ -olefins such as propylene, 1- butene, 1-hexene, 1-octene, and the like. Mixtures of olefins can be used. Ethylene and mixtures of ethylene with C 3 -C ⁇ o ⁇ -olefins are especially preferred.
• Many types of olefin polymerization processes can be used. Preferably, the process is practiced in the liquid phase, which can include slurry, solution, suspension, or bulk processes, or a combination of these. High-pressure fluid phase or gas phase techniques can also be used. The process of the invention is particularly valuable for solution and slurry processes.
• the olefin polymerizations can be performed over a wide temperature range, such as about -30°C to about 280°C. A more preferred range is from about 30°C to about 180°C; most preferred is the range from about 60°C to about 100°C.
• Olefin partial pressures normally range from about 15 psia to about 50,000 psia. More preferred is the range from about 15 psia to about 1000 psia.
• Catalyst concentrations used for the olefin polymerization depend on many factors. Preferably, however, the concentration ranges from about 0.01 micromoles per liter to about 100 micromoles per liter. Polymerization times depend on the type of process, the catalyst concentration, and other factors. Generally, polymerizations are complete within several seconds to several hours.
• Ligand Precursor Preparation 8-Methyl-5,10-dihydroindeno[1 ,2-b]indole (I), the ligand precursor of the catalyst prepared in Example A, is prepared by the method of Buu- Hoi and Xuong (J. Chem. Soc. (1952) 2225) by reacting p-tolylhydrazine with 1-indanone in the presence of sodium acetate/ethanol:

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